CN104152718B - A method for synchronously separating tin and iron from tin-containing iron tailings - Google Patents

A method for synchronously separating tin and iron from tin-containing iron tailings Download PDF

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CN104152718B
CN104152718B CN201410347393.3A CN201410347393A CN104152718B CN 104152718 B CN104152718 B CN 104152718B CN 201410347393 A CN201410347393 A CN 201410347393A CN 104152718 B CN104152718 B CN 104152718B
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CN104152718A (en
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姜涛
张元波
李光辉
苏子键
刘兵兵
陈军
范晓慧
黄柱成
郭宇峰
杨永斌
李骞
陈许玲
彭志伟
徐斌
甘敏
游志雄
周友连
杜明辉
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Central South University
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Abstract

本发明公开了一种含锡铁尾矿同步分离锡和铁的方法,该方法是将含锡铁尾矿原料和由硫酸钠、硼砂及黄腐酸钠按一定比例组成的复合添加剂混匀后,造块,干燥,再依次进行氧化焙烧、还原焙烧和磁选分离,获得锡残留量低于0.08%的铁精矿和品位大于1%的富锡尾矿,铁的回收率达到80%以上,实现了锡铁尾矿中铁和锡的高效分离;该方法污染小、成本低,且实现了含锡铁尾矿资源的深度综合利用,特别适用于处理锡铁共生关系紧密、采用现有选矿方法难以分离回收的含锡铁尾矿资源。The invention discloses a method for synchronously separating tin and iron from tin-containing iron tailings. The method comprises mixing the raw materials of tin-containing iron tailings and a compound additive composed of sodium sulfate, borax and sodium fulvic acid in a certain proportion. , agglomerated, dried, followed by oxidation roasting, reduction roasting and magnetic separation to obtain iron concentrates with less than 0.08% tin residue and tin-rich tailings with a grade greater than 1%, and the recovery rate of iron reaches more than 80%. , realized the high-efficiency separation of iron and tin in tin-iron tailings; this method has little pollution, low cost, and realizes the deep comprehensive utilization of tin-containing iron tailings resources, and is especially suitable for processing tin-iron symbiosis close relationship, using existing beneficiation The method is difficult to separate and recover tin-containing iron tailings resources.

Description

一种含锡铁尾矿同步分离锡和铁的方法A method for synchronously separating tin and iron from tin-containing iron tailings

技术领域technical field

本发明涉及一种含锡铁尾矿综合利用的方法,特别涉及一种从含锡铁选矿尾矿中采用先氧化焙烧再磁化焙烧的联合焙烧方法分离锡和铁的方法,属于矿物加工和有色冶金领域。The invention relates to a method for comprehensive utilization of tin-containing iron tailings, in particular to a method for separating tin and iron from tin-containing iron beneficiation tailings by using a combined roasting method of oxidation roasting and then magnetization roasting, which belongs to mineral processing and nonferrous metals metallurgical field.

背景技术Background technique

我国的锡矿资源典型的特点是:多为埋藏深、分布重叠的矽卡岩型脉锡矿床,锡石与硅、钙等脉石矿物以及多种金属矿物共生、伴生紧密,因而采矿、选矿以及冶炼的难度和成本高。目前国内锡矿储量约为300万吨,而可采储量仅为150万吨左右。由于长期开采和近几年地质工作的削弱,加之前些年小规模企业的无序开采,采用的选矿技术水平普遍不高,导致多数锡矿山后备资源不足,因而对我国锡资源的优势地位造成了潜在的威胁,严重影响了国内锡工业的健康持续发展。以目前我国锡资源的利用程度、产量与消耗的情况来看,锡矿资源保障年限不足20年。The typical characteristics of my country's tin ore resources are: most of them are skarn-type vein tin deposits with deep burial and overlapping distribution. And the difficulty and high cost of smelting. At present, the domestic tin ore reserves are about 3 million tons, while the recoverable reserves are only about 1.5 million tons. Due to the long-term mining and the weakening of geological work in recent years, coupled with the disorderly mining of small-scale enterprises in the past few years, the level of beneficiation technology adopted is generally not high, resulting in the lack of reserve resources in most tin mines, which has caused serious damage to the dominant position of tin resources in my country. The potential threat has seriously affected the healthy and sustainable development of the domestic tin industry. Judging from the current utilization degree, output and consumption of tin resources in my country, the guarantee period for tin resources is less than 20 years.

随着锡矿资源的日益枯竭以及金属锡价格的不断上涨,锡矿的可开采品位逐年下降,目前砂锡矿开采品位降低为0.009%~0.03%,最低仅0.005%,而脉锡矿开采品位为0.5%左右。With the depletion of tin ore resources and the rising price of metal tin, the minable grade of tin ore is decreasing year by year. At present, the mining grade of placer tin ore is reduced to 0.009%-0.03%, and the lowest is only 0.005%. It is about 0.5%.

经过长年选矿工艺处理,国内各大选矿厂累计的含锡尾矿总量达到5亿吨以上,并且还在以每年1000万吨以上的速度增加。含锡尾矿锡的平均品位在0.1%~0.2%,折合后金属锡的总量达到70万吨以上。据报道,仅云南云锡公司的含锡尾矿就达到2.4亿吨,其锡品位为0.18%左右,平均铁品位高于30%。After years of beneficiation process, the total amount of tin-containing tailings accumulated by major domestic beneficiation plants has reached more than 500 million tons, and is still increasing at a rate of more than 10 million tons per year. The average grade of tin in tin-containing tailings is 0.1% to 0.2%, and the total amount of metal tin after conversion reaches more than 700,000 tons. According to reports, the tin-containing tailings of Yunnan Yunxi Company alone reached 240 million tons, with a tin grade of about 0.18% and an average iron grade of more than 30%.

目前国内外关于锡石矿物的回收利用方法主要有重选、浮选和烟化挥发法(包括硫化挥发、氯化挥发以及还原挥发)。At present, the recycling methods of cassiterite minerals at home and abroad mainly include gravity separation, flotation and fuming volatilization (including sulfide volatilization, chlorination volatilization and reduction volatilization).

重选主要是利用锡石密度比共生脉石矿物大的特性,其生产成本低,环境污染小,是国内外生产锡石精矿的主要方法之一,目前世界锡产量有85%以上来自重力选矿。但由于砂锡矿含大量微细颗粒矿泥,分级脱泥是锡石重选过程中必要的准备作业,这一作业需严格控制入选粒级,尽量排除矿泥的干扰。但是锡矿砂的选别一般采用多段磨矿、选别相结合的工艺流程由于锡石脆性较大,磨矿过程中锡石极易过粉碎,使得微细粒随尾矿被丢弃,造成极大地资源浪费。Gravity separation is mainly to use the characteristic that the density of cassiterite is higher than that of paragenetic gangue minerals. Its production cost is low and the environmental pollution is small. It is one of the main methods of producing cassiterite concentrate at home and abroad. At present, more than 85% of the world's tin production comes from gravity Mineral dressing. However, since placer tin ore contains a large amount of fine-grained slime, classification and desliming is a necessary preparatory operation in the process of cassiterite gravity separation. This operation needs to strictly control the selected particle size and eliminate the interference of the slime as much as possible. However, the separation of tin ore generally adopts the process of combining multi-stage grinding and separation. Due to the high brittleness of cassiterite, cassiterite is easy to be crushed during the grinding process, so that the fine particles are discarded with the tailings, resulting in a huge waste of resources. waste.

浮选是针对嵌布粒度细、多种有价元素伴生复杂矿,在磨矿到单体解离后,可以有效回收微细粒的锡石。但是随着高品位锡矿资源日渐枯竭,浮选工艺需要处理的矿石贫、细、杂程度越来越高,浮选难度越来越大,并且对锡石的浮选往往同时需要考虑回收伴生的其它有价金属元素,因而浮选工艺面临微细颗粒含量多、矿浆pH、药剂制度等实际问题,增大了浮选难度,降低了产品回收率,导致锡的综合回收率多在30%以下甚至更低,浮选锡石选矿尾矿中仍含有0.1%~0.2%的锡未得到有效回收。因此,单一浮选法已经不能满足低品位锡矿回收的需要。Flotation is aimed at fine-grained and complex ores accompanied by various valuable elements. After the ore is ground to the dissociation of monomers, fine-grained cassiterite can be effectively recovered. However, with the depletion of high-grade tin ore resources, the ore that needs to be processed by the flotation process is becoming more and more poor, fine, and impurity, and the difficulty of flotation is becoming more and more difficult. In addition, the flotation of cassiterite often needs to consider the associated recovery. Therefore, the flotation process faces practical problems such as high content of fine particles, pulp pH, and chemical system, which increases the difficulty of flotation and reduces the product recovery rate, resulting in the comprehensive recovery rate of tin being below 30%. Even lower, the flotation cassiterite beneficiation tailings still contain 0.1% to 0.2% tin which has not been effectively recovered. Therefore, a single flotation method can no longer meet the needs of low-grade tin ore recovery.

硫化和氯化烟化挥发是目前处理低品位含锡铁资源较有效的方法,可以较好地实现锡铁分离,其主要原理是利用SnS以及SnCl2在高温下易挥发的特性,将含锡物料与还原剂、硫化剂或氯化剂混合均匀后置于高温下进行焙烧,焙烧过程中锡以亚锡化合物形式进入气相,在尾气中冷却并在烟尘进行回收。烟化挥发法的锡回收率较高,但是存在焙烧温度高,焙烧时间长,并且焙烧过程中形成SO2以及Cl2等有毒有害气体,不仅污染环境,对设备也存在腐蚀。以上缺陷严重限制了烟化挥发工艺的工业推广应用。专利“一种从选矿含锡尾矿中分离回收锡的方法(专利号:201210453731.2)”采用弱还原焙烧的方法处理传统选矿工艺难以处理的含锡选矿尾矿,使含锡尾矿中锡的挥发率达70%以上。其技术原理是:在高温条件之下,利用SnO2较易还原为SnO,且SnO的蒸气压大,从而实现SnO的挥发和回收。然而,该方法并没有涉及尾矿中铁元素的回收,且锡的回收率仍然不高。根据热力学分析,该方法焙烧气氛中CO的体积浓度[CO/(CO+CO2)]为20%~50%,该还原气氛条件下,高价铁氧化物易被还原为浮氏体,不利于后续铁元素的回收和利用。Vulcanization and chlorination fuming volatilization are currently more effective methods for treating low - grade tin-containing iron resources, which can achieve better separation of tin and iron. The material is evenly mixed with reducing agent, vulcanizing agent or chlorinating agent and then roasted at high temperature. During the roasting process, tin enters the gas phase in the form of stannous compound, is cooled in the tail gas and recovered in the smoke. The tin recovery rate of fuming volatilization method is high, but there are high roasting temperature and long roasting time, and toxic and harmful gases such as SO 2 and Cl 2 are formed during the roasting process, which not only pollutes the environment, but also corrodes the equipment. The above defects have seriously limited the industrial application of the fuming volatilization process. The patent "A method for separating and recovering tin from tin-containing tailings in mineral processing (Patent No.: 201210453731.2)" uses weak reduction roasting method to treat tin-containing mineral processing tailings that are difficult to handle by traditional mineral processing technology, so that the tin The volatilization rate is over 70%. The technical principle is: under high temperature conditions, the use of SnO 2 is easier to reduce to SnO, and the vapor pressure of SnO is large, so as to realize the volatilization and recovery of SnO. However, this method does not involve the recovery of iron in tailings, and the recovery rate of tin is still not high. According to thermodynamic analysis, the volume concentration [CO/(CO+CO 2 )] of CO in the roasting atmosphere of this method is 20% to 50%. Follow-up iron recovery and utilization.

综上所述,采用现有选矿工艺难以实现高效分离和回收共生关系复杂的锡铁资源,所得的锡回收率低,铁精矿中锡含量超过高炉冶炼用原料的要求(要求Sn含量低于0.08%),而烟化挥发工艺存在能耗高、成本高、污染大等缺点。因此,开发经济高效的利用含锡铁矿资源,尤其是储量丰富的难选含锡铁尾矿资源的工艺方法,可以有效缓解我国锡资源和铁矿资源供应紧张的局面。In summary, it is difficult to achieve efficient separation and recovery of tin-iron resources with complex symbiotic relationships by using the existing beneficiation technology, the resulting tin recovery rate is low, and the tin content in iron concentrate exceeds the requirements for raw materials for blast furnace smelting (requires Sn content below 0.08%), while the fuming volatilization process has the disadvantages of high energy consumption, high cost, and large pollution. Therefore, the development of economical and efficient utilization of tin-bearing iron ore resources, especially the rich reserves of refractory tin-bearing iron tailings resources, can effectively alleviate the tight supply of tin resources and iron ore resources in my country.

发明内容Contents of the invention

针对现有技术中处理锡铁尾矿工艺存在的分离效率低、成本高等一系列的缺陷,本发明的目的是在于提供一种以锡铁尾矿为原料,能实现锡铁尾矿中铁锡高效分离,污染小,成本低的方法,该方法实现了资源深度综合利用,满足工业生产要求。Aiming at a series of defects such as low separation efficiency and high cost in the process of processing tin-iron tailings in the prior art, the purpose of the present invention is to provide a kind of tin-iron tailings as raw material, which can realize high efficiency of iron and tin in tin-iron tailings. Separation, little pollution, and low cost, the method realizes the deep comprehensive utilization of resources and meets the requirements of industrial production.

本发明提供了一种含锡铁尾矿同步分离锡和铁的方法,该方法包括以下步骤:The invention provides a method for synchronously separating tin and iron from tin-containing iron tailings, the method comprising the following steps:

步骤(1):原料造块Step (1): Blocking of raw materials

将含锡铁尾矿与复合添加剂按质量比100:7~10混合后,将混合物料造块;所述的复合添加剂由以下质量百分比组分组成:硫酸钠10%~20%,硼砂50%~70%,黄腐酸钠20%~30%;After mixing the tin-containing iron tailings and the composite additive at a mass ratio of 100:7-10, the mixed material is agglomerated; the composite additive is composed of the following components in mass percentage: 10%-20% of sodium sulfate, 50% of borax ~70%, sodium fulvic acid 20%~30%;

步骤(2):氧化焙烧Step (2): Oxidation Roasting

步骤(1)所得团块经预干燥后,置于氧化气氛中,在800℃~900℃温度下进行氧化焙烧,得氧化焙烧团块;所述的氧化气氛由O2和N2混合组成,氧化气氛中O2的体积百分比分数[O2/(O2+N2)]×100%≥10%;The agglomerate obtained in step (1) is pre-dried, placed in an oxidizing atmosphere, and oxidized and roasted at a temperature of 800°C to 900°C to obtain an oxidized roasted agglomerate; the oxidizing atmosphere is composed of a mixture of O2 and N2 , The volume percentage of O 2 in the oxidizing atmosphere [O 2 /(O 2 +N 2 )]×100%≥10%;

步骤(3):磁化焙烧Step (3): Magnetization roasting

将步骤(2)所得氧化焙烧团块置于还原气氛中,在550℃~750℃温度下进行还原焙烧,还原焙烧完成后,在惰性气氛中进行冷却,得到还原焙烧产物;所述的还原气氛由CO和CO2混合组成,还原气氛中CO的体积百分比分数维持在5%≤[CO/(CO+CO2)]×100%≤25%;Place the oxidized and roasted agglomerate obtained in step (2) in a reducing atmosphere, and perform reduction and roasting at a temperature of 550° C. to 750° C. After the reduction and roasting is completed, cool in an inert atmosphere to obtain a reduction and roasting product; the reducing atmosphere Composed of a mixture of CO and CO 2 , the volume percentage of CO in the reducing atmosphere is maintained at 5%≤[CO/(CO+CO 2 )]×100%≤25%;

步骤(4):磨矿磁选Step (4): Grinding and Magnetic Separation

将步骤(3)得到的还原焙烧产物进行碾磨后,通过磁选分离得到磁铁精矿和富锡尾矿。After grinding the reduced roasted product obtained in step (3), magnetic separation is used to obtain magnetite concentrate and tin-rich tailings.

本发明的从含锡铁尾矿中同步分离锡和铁的方法还包括以下优选方案:The method for synchronously separating tin and iron from tin-containing iron tailings of the present invention also includes the following preferred schemes:

优选的方案中氧化焙烧时间为35min~65min。In a preferred solution, the oxidation roasting time is 35 minutes to 65 minutes.

优选的方案中还原焙烧时间为25min~65min。In a preferred scheme, the reduction roasting time is 25 minutes to 65 minutes.

优选的方案中步骤(4)中的还原焙烧产物碾磨直至粒度为-0.074mm所占质量百分比含量≥80%。In a preferred solution, the reduced roasted product in step (4) is ground until the particle size is -0.074 mm, and the mass percentage content is ≥ 80%.

优选的方案中步骤(4)中磁选分离是在磁场强度为800Gs~1500Gs的磁场中实现。In the preferred solution, the magnetic separation in step (4) is realized in a magnetic field with a magnetic field strength of 800Gs-1500Gs.

优选的方案中步骤(4)所得的磁铁精矿铁品位≥60%,锡含量<0.08%;所得的富锡尾矿中锡品位>1%。In the preferred scheme, the iron grade of the magnetite concentrate obtained in step (4) is ≥60%, and the tin content is <0.08%; the tin grade of the obtained tin-rich tailings is>1%.

所述的造块方法包括造球或压团。The agglomeration method includes pelletizing or briquetting.

本发明的创新之处在于:首先,本发明针对含锡铁尾矿中锡的物相进行了大量的研究,发现非锡石态锡的存在是采用选矿法分离回收含锡矿工艺中锡回收率低的重要原因。现有的选矿工艺普遍针对的是锡石(SnO2)矿物,对于非锡石态锡物相的回收几乎未被考虑,因而此类锡矿物在尾矿中得到富集。在部分含锡铁尾矿中,非锡石态的锡占总锡的质量百分含量甚至高于50%。发明人进一步的大量实验研究发现,非锡石态的锡矿物主要是水锡石和锡的硫化物相,在氧化焙烧条件下可发生分解或氧化反应,最终形成二氧化锡。同时发明人对含锡铁尾矿的焙烧过程做了大量的实验研究,发现由硼砂、硫酸钠和黄腐酸钠按一定比例组成的复合添加剂在氧化焙烧、磁化焙烧条件下,有助于强化锡、铁的分离,而且干燥和焙烧过程中团块能保证较好的形状,基本不产生粉末。因此,本发明最终确定以氧化焙烧、磁化焙烧和磁选分离相结合的方案,可以实现将尾矿中非锡石态锡物相转化为二氧化锡进入磁选尾矿中富集的同时,并将原尾矿中的高价铁氧化物还原成磁铁矿,再通过磨矿、磁选分离获得磁铁精矿。The innovation of the present invention lies in: firstly, the present invention has carried out a large number of researches on the phase of tin in tin-containing iron tailings, and found that the existence of non-cassiterite state tin is the recovery of tin in the process of separation and recovery of tin-containing ore by mineral processing. important reason for the low rate. The existing beneficiation processes are generally aimed at cassiterite (SnO 2 ) minerals, and the recovery of non-cassiterite tin phases is hardly considered, so such tin minerals are enriched in tailings. In some tin-bearing iron tailings, the mass percentage of non-cassiterite tin in the total tin is even higher than 50%. The inventors conducted a large number of further experimental studies and found that non-cassiterite tin minerals are mainly cassiterite and tin sulfide phases, which can undergo decomposition or oxidation reactions under oxidative roasting conditions, and finally form tin dioxide. At the same time, the inventor has done a lot of experimental research on the roasting process of tin-containing iron tailings, and found that the composite additive composed of borax, sodium sulfate and sodium fulvic acid in a certain proportion helps to strengthen the iron tailings under the conditions of oxidation roasting and magnetization roasting. The separation of tin and iron, and the agglomerates can ensure a better shape during drying and roasting, and basically no powder is produced. Therefore, the present invention finally determines the combination of oxidation roasting, magnetization roasting and magnetic separation separation, which can realize the phase conversion of non-cassiterite tin in the tailings into tin dioxide and enrich it in the magnetic separation tailings. And reduce the high-valent iron oxides in the original tailings to magnetite, and then obtain the magnetite concentrate through grinding and magnetic separation.

与现有技术相比,本发明的有益效果是:能使磁选铁精矿的铁回收率达到80%以上,其中锡残留量低于0.08%,满足高炉炼铁用原料的要求;锡主要以二氧化锡形式富集于尾矿中,可采用针对锡石矿物的现有选矿方法进行分离和回收。本发明与已有方法相比,本发明还具有焙烧温度低、时间短、锡铁分离效果显著等优点,特别适用于处理锡铁共生关系紧密、采用现有选矿方法难以分离回收的含锡铁尾矿。采用本发明所提供的技术,可以高效分离锡铁尾矿中的铁和锡,从而实现难选含锡铁尾矿的综合回收利用与增值加工。Compared with the prior art, the beneficial effect of the present invention is: the iron recovery rate of the magnetically separated iron concentrate can reach more than 80%, wherein the tin residue is less than 0.08%, which meets the requirements of raw materials for blast furnace ironmaking; tin mainly It is enriched in the tailings in the form of tin dioxide, which can be separated and recovered by the existing beneficiation methods for cassiterite minerals. Compared with the existing methods, the present invention also has the advantages of low roasting temperature, short time, and remarkable tin-iron separation effect, etc., and is especially suitable for treating tin-iron-containing iron that has a close symbiotic relationship and is difficult to separate and recover by existing beneficiation methods tailings. By adopting the technology provided by the invention, the iron and tin in the tin-iron tailings can be efficiently separated, thereby realizing the comprehensive recycling and value-added processing of the refractory tin-containing iron tailings.

附图说明Description of drawings

【图1】为本发明的工艺流程图。[Fig. 1] is a process flow diagram of the present invention.

具体实施方式Detailed ways

以下实施例旨在进一步说明本发明本内容,而不是限制本发明保护范围。The following examples are intended to further illustrate the content of the present invention, rather than limit the protection scope of the present invention.

对比实施例1Comparative Example 1

该对比实施例中没有添加本发明的复配添加剂,也没有进行氧化焙烧:Do not add composite additive of the present invention in this comparative example, also do not carry out oxidative roasting:

首先将含锡铁尾矿(锡品位0.45%,铁品位40.21%)脱水干燥至一定水分后进行造块,干燥;将干燥后的团块放入焙烧炉中,在600℃的焙烧温度下焙烧,通入还原性气体中CO的体积浓度[CO/(CO+CO2)]×100%为15%,焙烧时间65min,焙烧结束后,将焙烧团块在N2气氛下冷却后,磨细至80%小于0.074mm,在磁场强度为1000Gs条件下磁选,得到铁品位61.12%的铁精矿(其中锡的品位0.32%),铁回收率80.21%,得到富锡尾矿中锡的品位0.55%(其中66.3%的锡以二氧化锡存在)。锡铁分离效果差,磁选获得铁精矿含锡品位远高于0.08%,不能直接作为高炉炉料使用。First, dehydrate and dry the tin-containing iron tailings (0.45% tin grade, 40.21% iron grade) to a certain amount of water, then make agglomerates and dry them; put the dried agglomerates into a roasting furnace, and roast them at a roasting temperature of 600°C , the volume concentration [CO/(CO+CO 2 )]×100% of CO in the reducing gas is 15%, and the roasting time is 65min . To 80% less than 0.074mm, magnetic separation under the condition of magnetic field intensity of 1000Gs, to obtain iron concentrate with an iron grade of 61.12% (the grade of tin is 0.32%), the iron recovery rate is 80.21%, and the grade of tin in the tin-rich tailings is obtained 0.55% (66.3% of tin exists as tin dioxide). The separation effect of tin and iron is poor, and the tin grade of iron concentrate obtained by magnetic separation is much higher than 0.08%, so it cannot be directly used as a blast furnace charge.

对比实施例2Comparative Example 2

该对比实施例中添加了本发明的复配添加剂,但没有进行氧化焙烧:Added composite additive of the present invention in this comparative example, but did not carry out oxidative roasting:

首先将含锡铁尾矿(锡品位0.83%,铁品位34.21%)脱水干燥至一定水分后,配加占尾矿(干基)质量百分数7%的复合添加剂(不同组分的质量比例为硫酸钠:硼砂:黄腐酸钠=10%:70%:20%),将物料混合均匀后,造块,干燥;将干燥后的团块放入焙烧炉中,在550℃的焙烧温度下焙烧,通入还原性气体中CO的体积浓度[CO/(CO+CO2)]×100%为25%,焙烧时间65min,焙烧结束后,将焙烧团块在N2气氛下冷却后,磨细至80%小于0.074mm,在磁场强度为800Gs条件下磁选,得到铁品位60.23%的铁精矿(其中锡的品位0.33%),铁回收率81.14%,得到富锡尾矿中锡的品位1.02%(79.9%的锡以二氧化锡存在)。锡铁分离效果差,磁选获得铁精矿含锡品位远高于0.08%,不能直接作为高炉炉料使用。First, the tin-containing iron tailings (tin grade 0.83%, iron grade 34.21%) are dehydrated and dried to a certain amount of water, and then compound additives that account for 7% of the tailings (dry basis) by mass (the mass ratio of different components is sulfuric acid Sodium: borax: sodium fulvic acid = 10%: 70%: 20%), after mixing the materials evenly, agglomerate and dry; the dried agglomerate is put into a roasting furnace and roasted at a roasting temperature of 550°C , the volume concentration [CO/(CO+CO 2 )]×100% of CO in the reducing gas is 25%, and the calcination time is 65min . To 80% less than 0.074mm, magnetic separation under the condition of magnetic field strength of 800Gs, to obtain iron concentrate with an iron grade of 60.23% (the grade of tin is 0.33%), the iron recovery rate is 81.14%, and the grade of tin in the tin-rich tailings is obtained 1.02% (79.9% of tin exists as tin dioxide). The separation effect of tin and iron is poor, and the tin grade of iron concentrate obtained by magnetic separation is much higher than 0.08%, so it cannot be directly used as a blast furnace charge.

实施例1Example 1

首先将含锡铁尾矿(锡品位0.55%,铁品位40.21%)脱水干燥至一定水分后,配加占尾矿(干基)质量百分数10%的复合添加剂(不同组分的质量比例为硫酸钠:硼砂:黄腐酸钠=10%:70%:20%),将物料混合均匀后,造块,干燥;将干燥后的团块放入焙烧炉中,通入氮气保护,升温至900℃,待温度稳定之后,通入O2体积浓度[O2/(O2+N2)]×100%为10%混合气体焙烧35min,再降温至750℃,通入还原性气体中CO的体积浓度[CO/(CO+CO2)]×100%为5%,焙烧时间25min,焙烧结束后,将焙烧团块在N2气氛下冷却后,磨细至80%小于0.074mm,在磁场强度为1000Gs条件下磁选。得到铁品位64.31%的磁铁精矿(其中锡的品位0.05%),铁回收率83.11%,得到富锡尾矿中锡的品位1.12%(其中94.1%的锡以二氧化锡存在)。First, the tin-containing iron tailings (0.55% tin grade, 40.21% iron grade) are dehydrated and dried to a certain amount of moisture, and then compound additives that account for 10% of the mass percent of the tailings (dry basis) are added (the mass ratio of different components is sulfuric acid Sodium: borax: sodium fulvic acid = 10%: 70%: 20%), after the materials are mixed evenly, agglomerate, dry; the agglomerate after drying is put into roasting furnace, feed into nitrogen protection, be warming up to 900 ℃, after the temperature is stabilized, the volume concentration of O 2 [O 2 /(O 2 +N 2 )]×100% is 10% mixed gas for roasting for 35 minutes, and then the temperature is lowered to 750 ℃, and the CO in the reducing gas The volume concentration [CO/(CO+CO 2 )]×100% is 5%, and the calcination time is 25min. After the calcination is completed, the calcination agglomerate is cooled under N 2 atmosphere, and ground to 80% less than 0.074mm. Magnetic separation under the condition of intensity of 1000Gs. A magnetite concentrate with an iron grade of 64.31% (with a tin grade of 0.05%) was obtained, with an iron recovery rate of 83.11%, and a tin grade of 1.12% in tin-rich tailings (94.1% of which was present as tin dioxide).

实施例2Example 2

首先将含锡铁尾矿(锡品位0.83%,铁品位34.21%)脱水干燥至一定水分后,配加占尾矿(干基)质量百分数7%的复合添加剂(不同组分的质量比例为硫酸钠:硼砂:黄腐酸钠=20%:50%:30%),将物料混合均匀后,造块,干燥;将干燥后的团块放入焙烧炉中,通入氮气保护,升温至850℃,待温度稳定之后,通入O2体积浓度[O2/(O2+N2)]×100%为21%的混合气体焙烧40min,再降温至550℃,通入还原性气体中CO的体积浓度[CO/(CO+CO2)]×100%为25%,焙烧时间65min,焙烧结束后,将焙烧团块在N2气氛下冷却后,磨细至80%小于0.074mm,在磁场强度为800Gs条件下磁选,得到铁品位62.34%的铁精矿(其中锡的品位0.07%),铁回收率84.22%,得到富锡尾矿中锡的品位1.66%(其中94.3%的锡以二氧化锡存在)。First, the tin-containing iron tailings (tin grade 0.83%, iron grade 34.21%) are dehydrated and dried to a certain amount of water, and then compound additives that account for 7% of the tailings (dry basis) by mass (the mass ratio of different components is sulfuric acid Sodium: borax: sodium fulvic acid = 20%: 50%: 30%), after the materials are evenly mixed, agglomerate, dry; the agglomerate after drying is put into the roasting furnace, pass into nitrogen protection, be warming up to 850 ℃, after the temperature is stabilized, pass in a mixed gas with O 2 volume concentration [O 2 /(O 2 +N 2 )]×100% of 21% to roast for 40 minutes, then lower the temperature to 550 ℃, and pass in CO in reducing gas The volume concentration of [CO/(CO+CO 2 )]×100% is 25%, and the roasting time is 65min . Magnetic separation under the condition of a magnetic field strength of 800Gs, the iron concentrate with an iron grade of 62.34% (wherein the grade of tin is 0.07%), the iron recovery rate is 84.22%, and the grade of tin in the rich tin tailings is 1.66% (wherein 94.3% of tin present as tin dioxide).

实施例3Example 3

首先将含锡铁尾矿(锡品位1.13%,铁品位42.24%)脱水干燥至一定水分后,配加占尾矿(干基)质量百分数8%的复合添加剂(不同组分的质量比例为硫酸钠:硼砂:黄腐酸钠=15%:63%:22%),将物料混合均匀后,造块,干燥;将干燥后的团块放入焙烧炉中,通入氮气保护,升温至800℃,待温度稳定之后,通入O2体积浓度[O2/(O2+N2)]×100%为40%混合气体焙烧65min,再降温至700℃,通入还原性气体中CO的体积浓度[CO/(CO+CO2)]×100%为10%,焙烧时间55min,焙烧结束后,将焙烧团块在N2气氛下冷却后,磨细至80%小于0.074mm,在磁场强度为1500Gs条件下磁选。得到铁品位60.34%的铁精矿(其中锡的品位0.05%),铁回收率85.34%,得到富锡尾矿中锡的品位2.01%(其中96.5%的锡以二氧化锡存在)。First, the tin-containing iron tailings (1.13% tin grade, 42.24% iron grade) are dehydrated and dried to a certain amount of water, and then compounded with 8% of the tailings (dry basis) mass percentage (the mass ratio of different components is sulfuric acid Sodium: borax: sodium fulvic acid = 15%: 63%: 22%), after the materials are mixed evenly, agglomerate, dry; The agglomerate after drying is put into roasting furnace, feeds nitrogen protection, is heated up to 800 ℃, after the temperature is stabilized, the volume concentration of O 2 [O 2 /(O 2 +N 2 )]×100% is 40% mixed gas for roasting for 65 minutes, and then the temperature is lowered to 700 ℃, and the CO in the reducing gas The volume concentration [CO/(CO+CO 2 )]×100% is 10%, and the calcination time is 55min. After the calcination, the calcination agglomerate is cooled under the N 2 atmosphere, and ground to 80% less than 0.074mm. Magnetic separation under the condition of intensity of 1500Gs. An iron concentrate with an iron grade of 60.34% (with a tin grade of 0.05%) was obtained, with an iron recovery rate of 85.34%, and a tin grade of 2.01% in the tin-rich tailings (wherein 96.5% of the tin exists as tin dioxide).

实施例4Example 4

首先将含锡铁尾矿(锡品位1.02%,铁品位26.43%)脱水干燥至一定水分后,配加占尾矿(干基)质量百分数9%的复合添加剂(不同组分的质量比例为硫酸钠:硼砂:黄腐酸钠=17%:60%:23%),将物料混合均匀后,造块,干燥;将干燥后的团块放入焙烧炉中,通入氮气保护,升温至830℃,待温度稳定之后,通入O2体积浓度[O2/(O2+N2)]×100%为55%的混合气体焙烧50min,再降温至650℃,通入还原性气体中CO的体积浓度[CO/(CO+CO2)]×100%为20%,焙烧时间40min,焙烧结束后,将焙烧团块在N2气氛下冷却后,磨细至80%小于0.074mm,在磁场强度为1100Gs条件下磁选。得到铁品位60.34%的铁精矿(锡品位0.07%),铁回收率84.34%,得到富锡尾矿中锡的品位1.66%(其中95.8%的锡以二氧化锡存在)。First, the tin-containing iron tailings (1.02% tin grade, 26.43% iron grade) are dehydrated and dried to a certain amount of water, and then compound additives (the mass ratio of different components is sulfuric acid) that account for 9% of the tailings (dry basis) mass percentage are added. Sodium: borax: sodium fulvic acid = 17%: 60%: 23%), after the materials are mixed evenly, agglomerate, dry; The agglomerate after drying is put into roasting furnace, feeds nitrogen protection, is warming up to 830 ℃, after the temperature is stabilized, pass in a mixed gas with a volume concentration of O 2 [O 2 /(O 2 +N 2 )]×100% of 55% and roast for 50 minutes, then lower the temperature to 650 ℃, and pass in CO in reducing gas The volume concentration [CO/(CO+CO 2 )]×100% is 20%, and the roasting time is 40min. After the roasting is completed, the roasted agglomerate is cooled under N 2 atmosphere, and ground to 80% less than 0.074mm. Magnetic separation under the condition of a magnetic field strength of 1100Gs. An iron concentrate with an iron grade of 60.34% (tin grade 0.07%) was obtained, with an iron recovery rate of 84.34%, and a tin grade of 1.66% in the tin-rich tailings (wherein 95.8% of the tin exists as tin dioxide).

Claims (6)

1. a method for stanniferous iron tailings separated in synchronization tin and iron, is characterized in that, comprise the following steps:
Step (1): raw material agglomeration
After by stanniferous iron tailings, 100:7 ~ 10 mix in mass ratio with composite additive, by mixture agglomeration; Described composite additive is made up of following mass percent component: sodium sulfate 10% ~ 20%, borax 50% ~ 70%, SODLUM FULVATE 20% ~ 30%;
Step (2): oxidizing roasting
Step (1) gained agglomerate, after predrying, is placed in oxidizing atmosphere, carries out oxidizing roasting, obtain oxidizing roasting agglomerate at 800 DEG C ~ 900 DEG C temperature; Described oxidizing atmosphere is by O 2and N 2mixing composition, O in oxidizing atmosphere 2volume percent mark [O 2/ (O 2+ N 2)] × 100%>=10%;
Step (3): magnetizing roasting
Step (2) gained oxidizing roasting agglomerate is placed in reducing atmosphere, at 550 DEG C ~ 750 DEG C temperature, carries out reducing roasting, after reducing roasting completes, cool in an inert atmosphere, obtain reducing roasting product; Described reducing atmosphere is by CO and CO 2mixing composition, in reducing atmosphere, the volume percent fractal dimension of CO is held in 5%≤[CO/ (CO+CO 2)] × 100%≤25%;
Step (4): mill ore magnetic selection
After the reducing roasting product that step (3) obtains is milled, be separated by magnetic separation and obtain magnetite concentrate and rich tailing.
2. method according to claim 1, is characterized in that, the oxidizing roasting time is 35min ~ 65min.
3. method according to claim 1, is characterized in that, the reducing roasting time is 25min ~ 65min.
4. method according to claim 1, is characterized in that, described reducing roasting product is milled until granularity mass percentage content >=80% shared by-0.074mm.
5. method according to claim 1, is characterized in that, it is be realize in the magnetic field of 800Gs ~ 1500Gs in magneticstrength that described magnetic separation is separated.
6. the method according to any one of Claims 1 to 5, is characterized in that, magnetite concentrate Iron grade >=60% of gained in step (4), the mass content < 0.08% of tin; Tin grade > 1% in the rich tailing of gained.
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